Stabilization of fatty materials



TION or rs. Mamms Loran 0. Buxton, Maplewood, and Char-1w E.

Dryden, East Orange, N. J.,

assignors to Nopco Chemical Company, Harrison, N. 3., a co tion of NewJersey No Drawing. Application March 18, 1948,

: Serial N0. 655,003

a Cs. (on. rm-s1) invention will become apparent from the sub-2,396,681, granted March 19, 1946 (a division of Serial No. 431,700,filed February 20, 1942, now U. S. Patent No. 2,396,680, granted March19,-

1946), there are disclosed antioxidant concen trates which can beprepared from various types of oils which are particularly applicablefor the stabilization of fatty materials.

It has now been discovered that if antioxidants of the characterdescribed in the aforementioned patent are added to a fatty material andsimulsequent specification and claims.

The present invention can be applied to various types of fatty materialssuch as fatty oils.

fats, waxes, soaps, vitamin concentrates, etc. Thus, oilsand fats ofanimal, vegetable or fish origin, such as cod liver oil, as well asvitamin concentrates or vitamin-containing fractions obtained from suchoils; corn oi1,'cottonseed oil,'

soybean oil. and other vegetable oils; fats such as butter, margarine,lard, hydrogenated shorttaneously, or thereafter, the mixture of fattymaterial and antioxidant is treated with ammonia, the antioxidant effectis greatly enhanced. Furthermore, the antioxidant concentrates can betreated with ammonia and thereafter the ammonia-treated concentrates canbe added to fatty stances may be produced from components of the fattymaterial which, prior to ammonia treatment, have no antioxidant value.In addition to these antioxidants, new and better antioxidant components"are believed to be produced from the antioxidant concentrate disclosedin the aforementionedapplication.

It is, therefore, one of the objects of the Dresent invention to stablize various types of fatty materials against oxidation.

A second object of the present invention is to stabilize the vitaminvalues of fatty materials containing the same, as, for example,fishliver oils, by the addition of an antioxidant concentrate to thefish liver oil and thereafter treating the same with ammonia.

A third object of the invention is to form new antioxidant concentratesby treating antioxidant concentrates with ammonia.

'fatty mlbstances .which tend to become rancid.

enlngs, palm oil, etc.;' soapsof higher fatty acids; and compositionscontaining such fatty materials as essentialingredients, as for example.

cookies, cakes, crackers, breakfast cereals, etc v as well as foodemulsions such as mayonnaise, may all be suitably stabilized inaccordance with this invention. Furthermore, substances such assulfonated oils and other sulfonated fatty compounds, amides, monoanddlglycerides and other upon exposure to air may be treated in accordancewith the present invention. Other materials subject to change uponoxidation which can be treated include cosmetics such as face creams.hand lotions, shaving creams, etc.; gasoline, mineral oil, lubricatingoils, rubber, etc. The

amount of the extract added to the material to be stabilized may varyconsiderablydepending upon the activity of the extract and the degree ofinstability of the material to be stabilized. In general, from about0.1% to about 20%, Dreierably from about 0.5% to about'5%, ofantioxidant extract may be added to the oil or fat.

The present process is particularly applicable to the stabilization offat-soluble vitamin-containing oils or concentrates as well asvitamincontaining fractions recoverable from such prod= ucts by vacuumdistillation, solvent extraction or other processes.

Substances of a fatty nature stabilized in accordance with the presentinvention can be beated to elevated temperatures without substantiallyaffecting the activity of the antioxidants; moreover, the heating ofvitamin-containing oils so stabilized does not substantially reduce thevitamin activity of the oils.

The present process is applicable to antioxidant concentrates which areproduced-by solvent extraction from crude vegetable oils and similartypes of oils containing relatively large proportlons of antioxidant.Thus, vegetable oils and fats such as'soybean oil, wheat germ oil, corngerm oil,,corn oil, oat oil, rye oil, olive oil, sesame Other objectsand advantages of the present oil, cottonseedoil. palm oil. cocoabutter, palm kernel oil. coconut oil, rice oil, rice germ oil, seed oil,citicia oil, teaseed oil, perilla oil. alkalfa oil, celery seed oil,flax seed oil, groundnut oil,

hempseed oil, kapok oil, mustard seed oil, rapeseed oil, poppy seed oil,sunflower seed oil, pump- 'kin seed an; melon. seed oil, peanut oil andthe like can betreated. Another groupof fatty materials which can beemployed are .the fish liver oils such :as cod liver oil. tuna liveroil, halibut liver oil, -sh'ark liver oil, etc., as well as other 1. andis generally slightly more viscous than the marineoils such as -menhadenoil, herring oil "and sardineoil. Other oils which can be treated inaccordance with my invention are tomato seed oil, grape seed oil, peachkernel oil, 88 oil and whale oil. Preferably, the antioxidants areproduced-from vegetable oils.

The solvents which can be used in carrying out the process of theinvention include methanol and ethanol, either of which may contain anysuitable quantity of water or no water at all.

Moreover," 'a mixture of these two solvents may be used. A solvent sold.under the trade-mark f'Solox" by U. 8. Industrial Chemicals, Inc., wasfound to be quite efficacious in practicing this invention. The naturalantioxidants which it is desired to extract from the fatty materials aresoluble in methanol and ethanol at room temperature (10 C. to 30' C.)whereas the fatty materials'themselves are immiscible therewith orrelatively sot.

In carrying out the extraction of the antioxidants from the oils withwhich they are associated, theloil to be treated is first mixed with theparticular solvent to be employed. The relative proportion of oil tosolvent may vary widely; the. ratio of solvent to oii should be greaterthan one and. preferably, two to fifty parts of solvent to one partofoil. If desired. the solvent oil mass may be warmed to a temperatureslightly or substantially above room temperature.,, By so doing it issometimes possible to obtain somewhat more intimate contact of thesolvent with the fatty material and thereby obtain a more" emcient andcomplete extraction of the natural antioxidants. The solvent solutionand the fatty material can then be separated from each othenat theelevated temperature or the mixture can first be allowed to cool to roomtemperature before completing this step of the process. The extractionis preferably carried out in an atmosphere of inert gas.

The antioxidant fraction extracted from the oil may be recovered in anysuitable manner. As the solvent, and the oil are immiscible at room orat temperatures substantially above room temperature. they can beseparated by decantation, centrifugation or any other suitable means.The oil will generally be found to be'somewhat lighter in color thanoriginally and in many cases will have lostsome of its originalcharacteristic odor. Furthermore, in most cases it will be found thatmaterials responsible for producing break have been removed from the oilby the extraction. Thus the oil which has been extracted by the processof 'this invention can be used for a wide variety of purposes inaccordance with process well known to the art. Z

The solvent solution can be filtered and then treated to remove thesolvent therefrom, e. g., by vacuum distillation, whereby an extract isre covered containing relatively large .amounts of highly. activeantioxidants. If desired, water may be added to the extract in order toprecipitate some of the glycerides contained therein or original oil.Tests carried out on vegetable oil extracts indicate that the iodinevalues of the extracts are substantially lower than those of theoriginal oils. If a. vitamin-containing fish liver oil is employed inthe practice of the present invention, it will be found that the extractcontains a considerable portion of the vitamins concentrated therein.

Preferably, the fish liver oil and the like, having an antioxidantconcentrate of the character pre-. viously set forth added thereto, istreated with ammonia in the presence of a suitable solvent for the flshliver 011. Similarly, when an antioxidant concentrate is flrst treatedwith ammonia, a suitable solvent is preferably used. The solventemployed in the practice of this invention should be one in which thefatty material to be stabilized is readily soluble and/or theantioxidant concentrate is at least partially soluble. Thus, if a fishliver oil or concentrate prepared therefrom is being treated, ahydrocarbon or halogenated hydrocarbon solvent such as hexane, heptane,

, octane, ethylene dichloride, trichloroethylene, carbon tetrachloride,cyclohexane, methyl cyclohexane or benzene may be employed as the solvent, as well as solvents such as acetone, diacetone alcohol and thelike.

the above solvents may also be used. Thus a mixture of equal parts ofacetone and methanol has been found especially suitable.

The amount of solvent employed should be at least equivalent to and, insome instances, in excess of the amount of material bein treated. Theamountjof ammonia used in the process is relatively small as comparedtothe quantity of fatty-material or fish liver 011 bein treated and mayvary from about 1% to 20% by weight of concentrated aqueous ammonia ascompared to the weight of the fatty material. When gaseous ammonia orliquid ammonia is used, the amount is equivalent to that quantity ofconcentrated aqueous ammonia above 'set forth. It is to be understoodthat liquid or gaseous ammonia may be used in the present process. It isdesired to point out, therefore, that when in the specification andclaims the term ammonia is used, liquid or gaseous ammonia and ammoniadissolved in water or other suitable solvent therefor is intended. Ingeneral, the quantity of antioxidant concentrate which is added to thefish liver oil and the like is relatively small, being in theneighborhood of 2%, although in some instances from 0.1% to 20% may beused. Preferably, however, from 0.5% to about 5% of antioxidantconcentrate is sufficient to greatly enhance'the stability of fattymaterials of the character set forth.

It may be noted that where the antioxidant concentrate or extract istreated with ammonia before being added to the fatty material to bestabilized, the amount of ammonia used is equivalent to that just setforth, 1. e., approximately equal to and in some instances considerablyless than the weight of the concentrate. 1

some of the sterols may be removed: howeverfll The following examplesare intended to illus- Further, mixtures of trate the invention withoutin any way limiting the same:

Example I 500 grams of crude expeller soybean oil were admixed with 2000m1. of synthetic methanol and the mixture warmed to 50 C. in thepresence of nitrogen gas. The mass after reaching 50 C. was

agitated and then cooled to room temperature after which the solventsolution of the extracted material was separated from the oil. The oilwas again extracted in the manner set forth above and the two extractscombined and freed of methanol under reduced pressurein the presence 1of gaseous nitrogen. The yield of antioxidant ex tone, ammonia and waterwere then removed from the mass by distillation under reduced pressure.

Example II The same procedure as that set forth in Example I was carriedout with the exception that the use of acetone was dispensed with. Theshark liver oil containing the methanol extract was heated at 50 to 55C. for three hours using a long reflux condenser to prevent the escapeof ammonia.

The stabilized products produced according to Examples I and II werecompared with a blank of the same carbon-refined shark liver oil and asecond blank of the same 011 containing 3% of the methanol extract perse, producedaccording to the first half of Example I, by pouring 20grams of each oil in a separate 100 cc. beaker and storing these samplesat 36 C. in a dark oven. The vitamin A potency in each sample wasmeasured at' intervals as revealed in the following table:

Table Per cent Loss of Vitamin A after I pie 6 days 14 days 20days 1Carbon-refined shark liver oil contg. 56,400 A/gm 51.0

2 Sample 1 come ng 3% mathanoi extract 12. 2 28. 6 45. 5 3 Product ofExample 1.. 0. l4. 0 26. 0 4 Product oi Example II. 1. 5 l0. 6 25. 0

1. A process for producing an antioxidant for stabilizing fattymaterials which comprises contacting a crude fatty material containingnatural antioxidants with a solvent selected from the group consistingof methanol and ethanol, separating a. solution containing a highlyactive antioxidant extract from the remainder of the fatty material,recovering the antioxidant extract from the solvent solution thereof andcontacting said extract with ammonia to increase its antioxidantactivity.

2. The process of claim 1 wherein the antioxidant extract is contactedwith ammonia while dissolved in a fat solvent.

3. A process for stabilizing a fatty material prone to oxidation whichcomprises adding to the fatty material an antioxidant extract-producedby contacting a crude fatty material containing natural antioxidantswith a solvent selected from the group consisting of methanol andethanol, separating a solution containing a highly active antioxidantextract from the remainder of the fatty material and recovering theantioxidant extract from the solvent solution thereof-and contactingsaid fatty material containing said added antioxidant extract withammonia to increase the antioxidant activity of said extract.

4. The process of claim 3 wherein the fatty material containing theantioxidant extract is contacted with ammonia while dissolved in a fatsolvent.

5. The process of claim 3 wherein the fatty material containing theantioxidant extract is contacted with ammonia whil dissolved in acetone.

6. A process for stabilizing a fatty material containing a fat-solublevitamin which comprises adding to the fatty'material an antioxidantextractproduced by contacting a crude fatty material containing naturalantioxidants with a solvent selected from the group consisting ofmethanol and ethanol, separating a solution containing a highly activeantioxidant extract from the remainder of the fatty material andrecovering the antioxidant extract from the solvent solution thereof-andcontacting said fatty material containing said added antioxidant extractwith ammonia to increase the antioxidant activity of said extract.

'7; The process of claim 6 wherein the fatty material containing theantioxidant extract is contacted with ammonia while dissolved in a fatsolvent.

8. The process of claim 6 wherein the fatty material containing theantioxidant extract is contacted with ammonia while dissolved inacetone.

LORAN O. BUXTON. CHARLES E. DRYDEN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

